改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留

毕瑞锋; 邓锁成; 付萌; 张伟伟; 张义霞

doi:10.16801/j.issn.1008-7303.2021.0161

改进的QuEChERS-高效液相色谱-串联质谱法同时测定蔬菜水果中百菌清及其代谢物残留

doi: 10.16801/j.issn.1008-7303.2021.0161

毕瑞锋^{1, 2, ,},
邓锁成^{1, 2},
付萌¹,
张伟伟¹,
张义霞¹

1.
诺安实力可商品检验(青岛)有限公司，山东青岛 266012
2.
梅里埃营养科学集团（中国）研发部，山东青岛 266012

详细信息

通讯作者:
毕瑞锋，prefers@163.com.

中图分类号: O657.63；X592
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出版历程
- 收稿日期: 2021-08-10
- 录用日期: 2021-09-22
- 网络出版日期: 2021-10-26
- 刊出日期: 2022-04-01

Simultaneous determination of chlorothalonil and its metabolite in fruits and vegetables using modified QuEChERS-high performance liquid chromatography-tandem mass spectrometry

BI Ruifeng^{1, 2
, ,},
DENG Suocheng^{1, 2},
FU Meng¹,
ZHANG Weiwei¹,
ZHANG Yixia¹

1.
Sino Silliker Testing Services (Qingdao) Co., Ltd, Qingdao 266012, Shandong Province, China
2.
Mérieux NutriSciences (China) RD Department, Qingdao 266012, Shandong Province, China

摘要

摘要: 建立了同时检测蔬菜水果中百菌清及其代谢物4-羟基百菌清的高效液相色谱-串联质谱分析方法。样品经酸化乙腈提取后，采用配备大气压化学电离源的三重四极杆串联质谱仪测定。结果表明：百菌清及其代谢物4-羟基百菌清在0.005~0.2 mg/L范围内峰面积与质量浓度的线性关系良好，决定系数（R²）大于0.99；方法定量限为0.01 mg/kg。在0.01、0.05和0.2 mg/kg 3个添加水平下，百菌清及其代谢物4-羟基百菌清在结球甘蓝、黄瓜、葡萄和苹果4种基质空白样品中的平均回收率为83%~104%，相对标准偏差（RSD）为 0.73%~7.7% (n=6)。该方法简单快速、准确可靠，适合蔬菜水果中百菌清及其代谢物4-羟基百菌清的定量测定。
- QuEChERS /
- 高效液相色谱-串联质谱 /
- 大气压化学电离源(APCI) /
- 百菌清 /
- 4-羟基百菌清 /
- 蔬菜水果
Abstract: An analytical method for simultaneous determination of chlorothalonil and its metabolite chlorothalonil-4-hydroxy in fruits and vegetables was developed using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The samples were extracted by acidified acetonitrile, and the extraction solution was analyzed by HPLC-MS/MS equipped with APCI ion source. The results showed that good linearity was obtained in the range of 0.005-0.2 mg/L with correlation coefficients (R²) greater than 0.99. The limits of quantification were 0.01 mg/kg. At the spiked levels of 0.01, 0.05, and 0.2 mg/kg, the average recoveries in four sample matrices (cabbage, cucumber, grape, and apple) were 83%-104% with the relative standard deviations (RSDs) varying from 0.73% to 7.7% (n=6). The proposed method is simple, rapid, accurate and reliable, and it is suitable for the quantitative determination of chlorothalonil and its metabolite in fruits and vegetables.
- QuEChERS /
- high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) /
- atmosphere pressure chemical ionization(APCI) /
- chlorothalonil /
- chlorothalonil-4-hydroxy /
- fruits and vegetables

HTML全文

图 1 百菌清及其代谢物的MRM色谱图

Figure 1. MRM chromatogram of chlorothalonil and its metabolite

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图 2 酸度调节剂对目标分析物回收率的影响

1. No acidity regulator；2. 0.1 mL HAc + 1.5 g NaAc; 3. 0.1 mL 10% H₂SO₄; 4. 0.5 mL 10% H₂SO₄; 5. 1 mL 10% H₂SO₄; 6. 0.1 mL 10% H₃PO₄; 7. 0.5 mL 10% H₃PO₄; 8. 1 mL 10% H₃PO₄.

Figure 2. Effect of acid regulators on the recoveries of the target analytes

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表 1 百菌清及其代谢物的质谱参数

Table 1. Mass parameters of chlorothalonil and its metabolite

化合物 Compound	分子式 Molecular formula	母离子 Precursor ion, m/z	子离子 Product ion, m/z	去簇电压 DP/V	碰撞能量 CE/eV	碎片离子归属 Classification of fragment ion
百菌清	C₈Cl₄N₂	244.9	181.9^*	−100	−40	[M−Cl+O−Cl−CO]⁻
chlorothalonil			174.9	−100	−38	[M−Cl+O−2Cl]⁻
			209.9	−100	−32	[M−Cl+O−Cl]⁻
			146.9	−100	−51	[M−Cl+O−2Cl−CO]⁻
4-羟基百菌清	C₈HCl₃N₂O	244.9	181.9^*	−100	−40	[M−H−Cl−CO]⁻
chlorothalonil-4-hydroxy			174.9	−100	−38	[M−H−2Cl]⁻
			209.9	−100	−32	[M−H−Cl]⁻
			146.9	−100	−51	[M−H−2Cl−CO]⁻
注 (Note) ：^*定量离子 (Quantitative ion)。

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表 2 百菌清及其代谢物的线性方程、线性范围、决定系数和定量限

Table 2. Linear equations, linear ranges, R² and LOQs for chlorothalonil and its metabolite

化合物 Compound	线性方程 Linear equation	线性范围 Linear range/(mg/L)	决定系数 R²	定量限 LOQ/(mg/kg)
百菌清 chlorothalonil	y=230804.3x − 12.7	0.005~0.2	0.9985	0.01
4-羟基百菌清 chlorothalonil-4-hydroxy	y=397812.7x + 3.5	0.005~0.2	0.9990	0.01

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表 3 百菌清及其代谢物在4种基质中的添加回收率和相对标准偏差 (n=6)

Table 3. Recoveries and RSDs of chlorothalonil and its metabolite spiked in the four matrices (n=6)

基质 Matrix	添加水平 Spiked level/ (mg/kg)	百菌清 chlorothalonil		4-羟基百菌清 chlorothalonil-4-hydroxy
基质 Matrix	添加水平 Spiked level/ (mg/kg)	平均回收率 Average recovery/%	相对标准偏差 RSD/%	平均回收率 Average recovery/%	相对标准偏差 RSD/%
结球甘蓝 Cabbage	0.01	104	6.1	95	3.5
	0.05	94	2.3	85	2.5
	0.2	89	2.3	83	3.0
黄瓜 Cucumber	0.01	101	5.9	103	7.7
	0.05	99	4.6	100	2.9
	0.2	94	7.5	91	6.8
葡萄 Grape	0.01	93	3.5	95	3.7
	0.05	95	1.0	90	1.6
	0.2	88	1.3	87	0.73
苹果 Apple	0.01	83	2.6	100	4.2
	0.05	85	3.9	104	2.9
	0.2	84	3.9	103	4.6

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